DE102004040670A1 - Powdered pigment preparations for the color range from red to orange - Google Patents

Abstract

Powdery pigment preparations for the hue range from red to orange, corresponding to a CIELAB color angle h of -20 to 60 °, containing as essential components DOLLAR A (A) 20 to 99 wt .-% of at least one finely divided organic pigment selected from the group of Pyrazolone quinazolone pigments, isoindoline pigments, azo pigments, decetopyrrolopyrrole pigments and quinophthalone pigments, DOLLAR A and DOLLAR A (B) 1 to 80 wt .-% of at least one inorganic pigment having a Mohs hardness> = 5 DOLLAR A and by intensive dry mixing of the pigments (A) and (B) are available.

Description

• (A) 20 bis 99 Gew.-% mindestens eines feinteiligen organischen Pigments, ausgewählt aus der Gruppe der Pyrazolonchinazolonpigmente, Isoindolinpigmente, Azopigmente, Diketopyrrolopyrrolpigmente und Chinophthalonpigmente, und
• (B) 1 bis 80 Gew.-% mindestens eines anorganischen Pigments mit einer Mohsschen Härte ≥ 5

enthalten und durch intensives trockenes Mischen der Pigmente (A) und (B) erhältlich sind.The present invention relates to powdered pigment preparations for the hue range from red to orange, corresponding to a CIELAB color angle h of -20 to 60 °, which are essential components

• (A) from 20 to 99% by weight of at least one finely divided organic pigment selected from the group of pyrazolone quinazolone pigments, isoindoline pigments, azo pigments, diketopyrrolopyrrole pigments and quinophthalone pigments, and
• (B) 1 to 80 wt .-% of at least one inorganic pigment having a Mohs hardness ≥ 5

and obtainable by intensive dry mixing of the pigments (A) and (B).

It also concerns the invention a process for the preparation of these pigment preparations and their use for coloring of paints, printing inks, plastics, building materials and preparations of decorative cosmetics.

Pigment preparations, containing both organic and inorganic pigment, have been around for a while Time of particular interest as they offer the opportunity to take advantage organic pigments (high color strength, high color purity) to combine with those of inorganic pigments (good hiding power, high gloss). Commercially available are such pigment preparations so far only on basis of highly brilliant bismuth vanadate (C.I. Pigment Yellow 184) as inorganic Pigment and therefore can the requirements in terms of coloristic and durability fulfill. For the Hue range red to orange (-20 ° ≤ h ≤ 60 °) however, no satisfactory cheaper alternatives available.

In The patent literature describes various methods of preparation of mixtures of organic and inorganic pigments.

The U.S. Patent 4,226,634 relates to the common wet grinding of nickel titanium and titanium Nickel chrome yellow with organic yellow pigments or red pigments perylene based with glass beads under the action of shear forces. It It should be noted that the dry grinding of mixtures of these pigments with coatings significantly worse gloss and hiding power results.

Out US Pat. No. 4,222,788 is a process for preparing blends of nickel titanium and nickel chrome yellow with organic azo pigments in which the inorganic pigment is already known in the synthesis of the organic pigment is added. Here it is also stated that dry Mixing the finished pigments leads to pigment preparations, the Paintings with worse gloss result.

The EP-A-816 440 describes bismuth vanadate-based, yellow bis reddish yellow pigment powder mixtures by dry grinding of bismuth vanadate with the organic pigment.

Finally are from EP-A-985 712 yellow to reddish yellow, bismuth vanadate or rutile mixed phase pigments known pigment preparations in granular form, by aqueous milling of inorganic and organic pigment with glass beads and subsequent spray drying to be obtained.

Of the Invention was based on the object, pigment preparations for the color range Red to orange provide that versus a classic blend the individual, dispersed in paste form dispersed pigments a higher one color strength and thus have fertility.

• (A) 20 bis 99 Gew.-% mindestens eines feinteiligen organischen Pigments, ausgewählt aus der Gruppe der Pyrazolonchinazolonpigmente, Isoindolinpigmente, Azopigmente, Diketopyrrolopyrrolpigmente und Chinophthalonpigmente, und
• (B) 1 bis 80 Gew.-% mindestens eines anorganischen Pigments mit einer Mohsschen Härte ≥ 5

enthalten und durch intensives trockenes Mischen der Pigmente (A) und (B) erhältlich sind.Accordingly, pigment formulations have been found for the hue range from red to orange, corresponding to a CIELAB h color angle of -20 to 60 °, which are essential components

• (A) from 20 to 99% by weight of at least one finely divided organic pigment selected from the group of pyrazolone quinazolone pigments, isoindoline pigments, azo pigments, diketopyrrolopyrrole pigments and quinophthalone pigments, and
• (B) 1 to 80 wt .-% of at least one inorganic pigment having a Mohs hardness ≥ 5

and obtainable by intensive dry mixing of the pigments (A) and (B).

Furthermore, a process for the preparation of these pigment preparations was found which da characterized in that one mixes organic pigment (A) and inorganic pigment (B) intensively dry.

It was also the use of the pigment preparations for coloring paints. Printing inks, Plastics, building materials and preparations of decorative cosmetics found.

The Pigment preparations according to the invention are characterized in particular by their high color strength, the in paint up to 35% higher is as that of the individual drifts of the pigments, as well as the shine their paint finishes. The high color strength is essentially up attributed the fineness of the organic pigment (A), the by intensive mixing with the hard inorganic inorganic material acting as grinding media Pigment (B) is achieved. Thus, the mean particle size of the used organic pigments (A) before mixing generally at about 700 nm and after mixing at ≤ 500 nm, especially at ≤300 nm.

there is surprising that this Effect in the pigment preparations of the invention when dry mixing and without the use of grinding media or other grinding aids is achieved. This is especially true in the With regard to US Pat. No. 4,226,634 which repeats indicating that only by wet milling using glass beads to achieve high color strengths and high gloss are.

In particular, surprisingly is also that the Pigment preparations according to the invention despite the fineness of the organic pigment contained (A) essentially unchanged Weather fastness and chemical resistance show how they interact with increasing reduction of the particle size of the organic pigment would have been expected.

The in the pigment preparations according to the invention inorganic pigment contained as component (B) has a Mohs hardness ≥ 5, preferably ≥ 6, on.

Especially suitable as component (B) are inorganic pigments from the group Rutile and rutile mixed phase pigments, wherein the rutile mixed phase pigments are preferred.

It can all known pigments are used. Examples are listed with coloring ions of the metals nickel, chromium, manganese, iron and / or niobium-doped rutile pigments.

Of course, different ones be included inorganic pigments (B).

Prefers is the color of the inorganic pigments (B) at least in the Near the for the Pigment preparation desired Tonal range. So it is mainly yellow or brown pigments used.

in the As particularly suitable pigments (B), C.I. Pigment Yellow 53, 157, 158, 159, 160, 161, 162, 163, 164 and 189 as well as C.I. Pigment Brown 24 and 33 as well as C.I. Pigment White 6. Preference is given in particular to C.I. Pigment Brown 24 and next to it also C.I. Pigment Yellow 42.

at in the pigment preparations according to the invention The organic pigment contained as component (A) is a pyrazolone quinazolone pigment, an isoindoline pigment, an azo pigment Diketopyrrolopyrrolpigment or a Chinophthalonpigment.

Of course you can too various organic pigments (A) may be included.

Also its color is preferably at least close to that for the pigment preparation desired Color range, so that in particular Red, orange and yellow pigments are used, the yellow pigments preferably combined with red or orange pigments.

• – Pyrazolonchinazolonpigmente: C.I. Pigment Orange 67 und C.I. Pigment Red 216;
• – Isoindolinpigmente: C.I. Pigment Yellow 139 und 185; C.I. Pigment Orange 61 und 69; C.I. Pigment Red 260;
• – Azopigmente: C.I. Pigment Yellow 2, 13, 62, 74, 151, 168 und 191; C.I. Pigment Orange 5, 13, 34, 36, 64 und 67; C.I. Pigment Red 1, 2, 3, 4, 5, 23, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 51:1, 51:1, 53, 53:1, 57:1, 58:2, 58:4, 112, 144, 146, 148, 166, 170, 184, 214, 220, 221 und 251.
• – Diketopyrrolopyrrolpigmente: C.I. Pigment Orange 71; C.I. Pigment Red 254, 264 und 272;
• – Chinophthalonpigmente: C.I. Pigment Yellow 138.

Particularly suitable examples of the individual pigment classes are:

• - Pyrazolonequinazolone pigments: CI Pigment Orange 67 and CI Pigment Red 216;
• Isoindoline pigments: CI Pigment Yellow 139 and 185; CI Pigment Orange 61 and 69; CI Pigment Red 260;
• - azo pigments: CI Pigment Yellow 2, 13, 62, 74, 151, 168 and 191; CI Pigment Orange 5, 13, 34, 36, 64 and 67; CI Pigment Red 1, 2, 3, 4, 5, 23, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 51: 1, 51: 1, 53, 53: 1 , 57: 1, 58: 2, 58: 4, 112, 144, 146, 148, 166, 170, 184, 214, 220, 221 and 251.
• Diketopyrrolopyrrole pigments: CI Pigment Orange 71; CI Pigment Red 254, 264 and 272;
• - Quinophthalone pigments: CI Pigment Yellow 138.

Prefers are especially C.I. Pigment Yellow 139, C.I. Pigment Orange 67 and C.I. Pigment Red 170.

The the component (A) of the pigment preparations according to the invention forming organic pigment is present in the pigment preparations according to the invention finely divided form. Usually it has mean particle sizes ≤ 500 nm, preferably ≤ 300 nm.

The Pigment preparations according to the invention contain 20 to 99 wt .-%, in particular 30 to 70 wt .-%, of the organic Component (A) and 1 to 80 wt .-%, especially 30 to 70 wt .-%, the inorganic component (B).

The Pigment preparations according to the invention are advantageous according to the production method likewise according to the invention to obtain the organic pigment (A) and inorganic pigment (B) are mixed thoroughly dry.

The inorganic pigment (B) acts as a grinding medium for the organic pigment (A) and thus causes comminution of the organic pigment particles.

At the inventive method can both the crude pigments obtained during pigment synthesis and Pigments which already have a pigment finish, i. a setting of particle shape and size have been used.

For the inventive method It is advantageous that no additional grinding media or other grinding aids used and thus also of the pigment preparation must be disconnected. Still unnecessary also a drying step, since there is no solvent during mixing is used.

to execution the method according to the invention are suitable technical apparatus, in which organic and inorganic Pigment are mixed so intensively that the hard inorganic pigment (B) as a grinding media for the organic pigment (A) can act.

This Shear mixing may e.g. in mixers, such as Lödige mixers, Eirich mixers and Ruberg mixers.

The Grinding action of the inorganic pigment (B) can be further enhanced by that the mixing apparatus other internals, e.g. rotating at high peripheral speed Cutter heads, which increase the shear forces acting on the organic pigment (A). The above mixer can e.g. with such cutterheads equipped become.

The grinding action of the inorganic pigment is also used in apparatus strengthened which cause additional shear by using heavy weights. A particularly suitable example of this is a Koller. By the slowly rotating Kollersteine a strong mechanical contact pressure is generated, which promotes the grinding action of the inorganic pigment.

Usual mixing times are e.g. when using a Lödige mixer at 5 to 60 min and when using a Koller at 0.5 to 10 h.

Especially when using a skimmer, it is used to loosen up baked Pigment recommended, to the mixing process a short grinding step to join, e.g. a passage through a pin mill, which usually takes <1 min.

The Pigment preparations according to the invention are great for coloring of paints, printing inks, plastics, building materials and preparations suitable for decorative cosmetics. They are characterized by this their beneficial coloristic properties, especially their high color strength and their brilliance, and their high durability, especially weather fastness and chemical resistance, out.

Examples

1) Preparation of Pigment Preparations According to the Invention

• Variant Ia: x ₁ parts by weight of organic pigment (A) and y _{1 part by} weight of inorganic pigment (B) were mixed for 15 minutes in a Lödige mixer with rotating cutter heads.
• Variant Ib: x ₁ parts by weight of organic pigment (A) and y _{1 part by} weight of inorganic pigment (B) were mixed for 15 minutes in a Lödige mixer without rotating cutter heads.
• Variant IIa: x ₁ parts by weight of organic pigment (A) and y _{1 part by} weight of inorganic pigment (B) were processed t, h in a Koller. The resulting product was then ground briefly (10 sec) in a pin mill (pitch of pins 14.5 cm).
• Variant IIb: x ₁ parts by weight of organic pigment (A) and y _{1 part by} weight of inorganic pigment (B) were processed for ₁ h in a Koller. Then a further ₂ parts by weight of inorganic pigment (B) were added and further t ₂ h were processed in the Koller. The resulting product was then ground briefly (10 sec) in a pin mill (pitch of pins 14.5 cm).

Further Details of these experiments are shown in Table 1.

Table 1

2) Testing of Pigment Preparations According to the Invention

The evaluation of the coloristic properties was carried out on paints which were prepared as follows:
A mixture of 50 g of the respective pigment preparation and 200 g of alkyd melamine stoving enamel (45% by weight solids) was shaken with 300 g glass beads (3 mm diameter) for 90 min with a Skandex instrument, then applied to aluminum Q panels (Film Extractor Type 238 II, Erichsen) and baked at 130 ° C for 30 min.

The Determination of the color angle H * was carried out with a spectrophotometer Spectrolino (Gretag-Macbeth) made.

The Determination of color intensity (Indication of the coloring equivalents FAE, DIN 53235) was colorimetrically determined by the white whitening of the paint. To 200 g of alkyd-melamine stoving enamel with 50 g of titanium dioxide 2310 (Kronos) and 5 g of the respective pigment preparation with 300 g glass balls (3 mm diameter) shaken for 90 min with a Skandex device, then applied opaque on aluminum Q panels (film extractor type 238 II, Erichsen) and 30 min at 130 ° C baked.

The respective analogous coatings, which were produced from individual abrasions of the organic and inorganic pigments: V Orange: 10 parts by weight CI Pigment Yellow 139, 31.5 parts by weight CI Pigment Orange 67, 58.5 parts by weight CI Pigment Brown 24 V red: 63 parts by weight CI Pigment Red 170, 36 parts by weight CI Pigment Brown 24, 1 part by weight CI Pigment Yellow 42 the FAE value has been assigned 100 (default). FAE values <100 mean a higher color intensity than the standard, FAE value> 100 correspondingly a smaller color intensity.

to Determination of the weather fastness were the lacquered sheets 2000 h long in a Xenotest 1200 (device from Heraeus) according to EN ISO 4892-2 loaded. The color change The weathered sheets were then assessed according to the gray scale according to ISO 105-A02. These Scale ranges from grade 5 (unchanged finish) to grade 1 (heavily modified Paint).

The Results of these tests are summarized in Table 2.

Table 2

Claims (7)

powdery Pigment preparations for the color range from red to orange, according to a CIELAB Color angle h of -20 up to 60 °, as essential components (A) 20 to 99% by weight at least a finely divided organic pigment selected from the group of pyrazolone quinazolone pigments, Isoindoline pigments, azo pigments, diketopyrrolopyrrole pigments and quinophthalone, and (B) 1 to 80% by weight at least an inorganic pigment having a Mohs hardness ≥ 5, included and by intensive dry mixing of the pigments (A) and (B) are obtainable. Pigment preparations according to claim 1, which are used as component (B) at least one pigment from the group rutile and rutile mixed phase pigments contain. Pigment preparations according to claim 1 or 2, which as component (A) at least one organic pigment with a average particle size ≤ 500 nm included. Process for the preparation of pigment preparations according to claims 1 to 3, characterized in that organic pigment (A) and inorganic pigment (B) intensely dry mixed. Method according to claim 4, characterized in that that he it in a Koller or a mixer, built into the cutterheads could be, performs. Method according to claim 4, characterized in that that he do it in a Koller and a short grind in a pin mill connects. Use of pigment preparations according to claims 1 to 3 for coloring of paints, printing inks, plastics, building materials and preparations of decorative cosmetics.